Process for producing improving



Patented Feb. 11, 1941 UNITED STATES,

PROCESS FOR. PRODUCING. IMPROVING PRODUCTS FOR PELTS, FURS, HAIRS, AND TEXTILES OF ALL KINDS Elmar Profit, Berlin-Llchterfelde, Germany, as-

signor to Vereinig'te Glanzstofl-Fabrieken A.-G., Wuppertal-Elberfeld, Germany, a corporation of Germany No Drawing. Application February 7, 1938, Se-

rial, No. 189,275. In Germany February 11, 193

Claims. (01. 260-513) This invention .relates to a process for producing improving products for pelts, furs, hairs, and textiles of all kinds.

As is well known the readily soluble alkali salts 5 of aliphatic monocarboxylic acids form the basis of the usual washing process. The said salts, commonly referred to as washing soaps, possess however, as was already known, a series of drawbacks since the substances referred to on the one hand are very readily decomposed with flocculation by means of acids, such as for example sul-. phuric acid, and on the other hand they are flocculated out bythe hardness formers of water, such as calcium, magnesium; and the like, with formation of insoluble alkaline earth metal soaps. The usual washing soaps also show similar drawbacks when they are usedas scrooping, softening, fulling, wetting, foaming, cleansing, and emulsifying agent, e. g. for treating pelts, furs, hairs, textiles of all kind, such as wool, silk, cotton, flax, artificial silk, cellulose wool and the like. The preparation of soluble compounds of aliphatic nature which act similarly to the known soaps for washing purposes and other, e. g. textile, purposes, but do not possess the said disadvantages of decomposition inacid medium or flocculation out in the present of alkaline earths, has therefore been an old problem of the chemical improving art.

cetyl alcohol obtainable from spermaceti,- 'which was converted in turn into the iodide, the sulphur compound, and finally by oxidation into cetyl sulphonic acid. This classical way which leads actually to the true sulphonic acid, unfortunately possesses the drawback that it starts out from an expensive raw material which can be procured only in comparatively limited quantity and which ought to be reserved for other purposes of use. Finally, carrying out the chemical, change through the iodide is also very expensive.

A direct way has, however, also been-tried, by directly treating solar oil with fuming sulphuric acid. It is true that in this way aliphatic sulphonic acids are obtained, but the direct employment of the radical agent is accompanied by an extensive resinification and even carbonising of the paraflin compounds and consequently dark colouring of the products obtained, so that the utilisation of this way on an operative scale had for the most part to be given up again.

It will be gathered from the historical development and the foregoing example. with which the industry has already concerned itself, that there exists agreat interest in the production and use One attempt in this direction set out from of such sulphonic acids. In actuality, in contradistinction to the classical washing and setting agents, they are characterised by the fact phonic acids in practical use.

Below a new way is describedwhich is characterised by the fact that a start is made from a cheap natural product occurring in unlimited quantities and nevertheless a good and satisfactorily acting end product in the form of a mixture of aliphatic sulphonic acids is obtained without the starting product or its derivatives undergoing any appreciable decomposition or carbonising in the course of the procms. The new process starts out from mineral oil, crude or purified, or from individual fractions of mineral oil, e. g. from petroleum, or some other fraction of mineral oil.

. The mineral oil portion or fraction is first of all chlorinated, preferably to an extent such that chiefly monochlorparafiins are, formed.-

From investigation of the mineral oil portion in question as regards the boiling points of the individual fractional portions one can calculate out the approximate average molecular weight and accordingly calculate beforehand the necessary chlorine absorption and subsequently measstances, with assistance of cooling.

The chlorination mixture is thereupon treated with hydrosulphides (NaSH) or soluble sulphides (NazS). The mercaptans or sulphides produced are then oxidised by means of a powerful oxidising agent, such as for example nitric acid.

By choice and concentration of the oxidising agent, as well as the temperature, the oxidation can be conducted so that pre-eminently the sought aliphatic true sulphonic acids are formed.

.If the oxidation is carried out to a limited extent by choice of a milder oxidising agent or by reducing the concentration of the same, or by moderating the reaction temperature, then, in addition to the sulphonic acids, amongst other things also disulphides are formed, and it is even possible by limitation of the oxidation as indialkali sulphites, more particularly in the hot and under pressure. In this way the corresponding alkali sulphonates are obtained.

Example I Chlorinated petroleum, prepared by leading chlorine into the technical fraction 160-280 C. and which contains 21 parts by weight of chlorme substantially in the form of monochlorides, is mixed in a quantity of 2 kg. with'an alcoholic KSH solution. The latter solution consists of 5 litres of denatured alcohol in which 1.5 kg. of KSH have been dissolved. The mixture is heated to boiling for 5 hours under reflux, and thereupon the oily mercaptans are separated off from the alcoholic treatment liquid in almost quantitative yield. 1.9 kg. of themercaptans obtained are now treated little by little with 8 kg. of 30% nitric acid under reflux whilst heating up to the disappearance of the oil. The

aqueous solution obtained is evaporated down up to the point of removal of the retained nitrous compounds and of the water. The product obtained is a semi-solid light brown water solubl'e mass permeated with crystals, and contains the desired sulphonic acids.

Example II The mercaptans obtained according to Example I are mixed in a quantity of 1.9 kg. with 15 kg. of diluted 15% nitric acid and heated under reflux for 4 to 5 hours. The light yellow oil floating on the top is separated off from as in Example I in order to expel water and volatile nitrous products. The residue contains the sulphonic acids described in Example I.

Example III The petroleum chlorinated as in Example I is treated in a quantity of 2 kg. with 13 kg. of

sodium sulphite solution which contains 1.3 kg. of sodium sulphite (NazSOa) and the mixture is heated in autoclaves to 150-160 C. for hours. The non-interacted chlorination products of the petroleum form the upper layer of the treatment liquid and are separated from the aqueous portions in a separating funnel and if necessary or desired subjected to a renewed treatment either alone or in admixture with further chlorination products of petroleum. The aqueous portions separated off contain the sought sulphonic acids in the form of the sodiumsalts and may be evaporated down to dryness. The chlorination products of the mineral oil,

more particularly of petroleum, may. also be interacted with potassium sulphite or ammonium sulphite to form the corresponding alkali sulphonates.

ExampZe IV The mercaptans obtained under Example I are, in a quantity of 1 kg., stirred up with 28 L litres of water to which 1.75 kg. of commercial potassium permanganate has previously been added. The mixture is boiled at atemperature not exceeding 100 C. until the oily parts have disappeared. The interaction is generally flnished in about flve hours. The reddish solution, which still contains unused potassium permanganate, is decomposed in the hot with the necessary quantity of oxalic acid in order to destroy.

the potassium permanganate remaining over. The manganese dioxide separated out is removed from the solution by filtration. The colorless solution contains the sought sulphonic acids in the form of the potassium ,salts and may be concentrated by evaporation.

In spite of the fact that the starting product, namely mineral oil and its fractions, is not a unitarily defined body, but is a natural mixture of numerous paraflin bodies and parafifin-like bodies, it has been found that nevertheless end products can be obtained in the sulphonation process which are quite usable for the various technical purposes indicated. This is the more surprising since the starting products themselves are not a mixture of pure normal parafiins, and therefore are not merely a more or less large section of a homologous series of the same, but comprises also secondary and tertiary parafiins, and even unsaturated olefinic-like compounds. Finally it is also noteworthy that in all mineral oils and fractions thereof, including those from American sources, there are still certain quantities of aromatic compounds.

In spite of this complex and variable composition of the starting products, it is 'possible, as numerous experiments have shown, to obtain within the scope of the present process light colored products utilisable with advantage in the technics. In the majority of cases the products can be obtained in high yield. It is particularly remarkable that by certain of the sulphonation methods, more particularly by the oxidation of the corresponding mercaptans, also disulphides or mixtures of the same are obtained which are characterized by a particularly good wetting action. "The disulphide-mixture obtained from the mineral oil and its fractions is an oil-like, light yellow product of great stability towards acids.

Theproducts obtained are suitable for the most diverse purposes, for treating pelts, furs, hairs, textiles, such as wool, silk, cotton, flax, artificial silk, cellulose wool and the like. They may be used for this purpose as scrooping and softening agents and for improving the fullness. They have for the most part an outstanding wetting and frothing action which makes them suitable for use in other industries as well. They possess satisfactory cleansing powers and have proved to be outstanding emulsifying agents. They also possess a noteworthy fatsplitting action.

Having now set forth the invention as required by the patent statutes, what is claimed is:

1. A process for making an agent for treatment of pelts, furs, hairs and textiles of all kinds, comprising heating the halogenated product of mineral oil with a substance selected from the group consisting of hydrosulfides and sulfides and then reacting the sulfhydrated product with not of mineral oil with a hydrosnlfide to form mercaptans and then reacting the mercaptans with an oxidizing agent to form the corresponding sulfonic acids.

3. A process as claimed in claim 2, wherein the oxidizing agent consists of nitric acid.

4. A process as claimed in claim 2. wherein the oxidizing agent consists of a permanganate. 5. A process as claimed in. claim 2, wherein the oxidizing agent consists of hydrogen peroxide.

ELMAR PROFFT. 

